Thermal Decomposition of CxF2 x+1C(O)OONO2(x = 2, 3, 4)

The atmospheric degradation of molecules containing the CxF2x+1C(O) moiety, such as perfluoroaldehydes CxF2x+1C(O)H (x = 2-4) formed in the degradation of telomeric alcohols, could lead to the formation of perfluoroacyl peroxynitrates CxF2x+1C(O)OONO2. The thermal decomposition of the CxF2x+1C(O)OONO2 family (x = 2, 3, 4) was investigated by infrared spectroscopy and computational models. Each peroxynitrate synthesis was performed through the photolysis of gas mixtures of the corresponding perfluoroaldehyde, chlorine, nitrogen dioxide, and oxygen. Kinetic analysis for the thermal decomposition of peroxynitrates were performed in the range from 297.0 to 313.7 K at a total pressure of 1000 mbar and the activation energy was experimentally determined. Experimental data were complemented with theoretical data using the Gaussian09 Program Suite. The structures of peroxynitrates were optimized using DFT methods. The activation energies were calculated and investigated taking into account the stereoelectronic effects and using theoretical calculations as well as NBO analysis. The influence of anomeric interaction over the O-N bond was evaluated for all the molecules. Analysis of the results shows that CxF2x+1C(O)OONO2 stability is independent of CxF2x+1 chain length, in contrast to the behavior for perfluoroalkyl peroxynitrates (CxF2x+1OONO2).Fil: Vila, Jesús Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Iriarte, Ana Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Chiappero, Malisa Susana. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; ArgentinaFil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Evaluation of the influence of filter medium composition on treatment performances in an open-air green wall fed with greywater.

Abstract According to the European Research and Innovation Policy Agenda, nature-based solutions (NBSs) are key technologies to improve the sustainability of urban areas. Among NBSs, green walls have been recently studied for several applications, among the others the treatment of lowly polluted wastewater flows as greywater (GW, e.g. domestic wastewater excluding toilet flushes). This work is aimed at the evaluation of the influence of four additives (compost, biochar, granular activated carbon, polyacrylate) mixed with a base filter medium made of coconut fibre and perlite, on the performances of a green wall fed in batch mode with synthetic GW. The green wall was operated with a high hydraulic loading rate of GW (740.8 L/m2/day) in open-air winter conditions (3.5–15 °C measured for GW) between January and April. The performances of the green wall have been assessed though the monitoring every 1–2 weeks of physicochemical and biological parameters (pH, electric conductivity, total suspended solids, dissolved oxygen, BOD5 and COD, nitrogen and phosporus compounds, chlorides and sulphates, anionic surfactants and E. coli). Removal performances were excellent for BOD5 (>95%) and E.coli (>98%) for all additives; compared to the base medium, biochar was the best performing additive over the highest number of parameters, achieving removals equal to 51% for COD, 47% for TKN and nitric nitrogen and 71% for anionic surfactants. Compost also achieved high removal performances, but the frequent clogging events occurred during the monitoring period do not make its use recommendable. Granular activated carbon and the combination of biochar and polyacrylate performed better than the base medium, but only about the removal of nitric nitrogen. These results demonstrated that, in the considered experimental boundaries, biochar could improve the overall treatment performances of a green wall fed by GW and operated in challenging conditions

Thermal Stability of Peroxy Acyl Nitrates Formed in the Oxidation of CxF2x+1CH2C(O)H (x = 1,6) in the Presence of NO2

The formation of CxF2x+1CH2C(O)OONO2 (x = 1,6) from the photooxidation of CxF2x+1CH2C(O)H (x = 1,6) in the presence of NO2 was investigated. The infrared spectrum of C6F13CH2C(O)OONO2 is reported for the first time, and thermal stability for both peroxynitrates at 295 K and 9.0 mbar is informed. Kinetic parameters (activation energy and pre-exponential factor) for CF3CH2C(O)OONO2 at 9.0 and 1000 mbar are: 108 ± 2 kJ/mol, 1.5 × 1015 and 114 ± 2 kJ/mol, 2.4 × 1016, respectively. A comparison is made between fluoro and hydrogenated peroxy acyl nitrates.Fil: Henao Arboleda, Diana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Chiappero, Malisa Susana. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Argüello, Gustavo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Photochemistry and absorption cross-sections temperature dependence of trifluoromethoxycarbonyl peroxy nitrate (CF3OC(O)OONO2)

The photochemical rupture of CF3OC(O)OONO2 at 254 nm leads to the formation of NO2 + CF3OC(O)OO, and NO3 + CF3OC(O)O radicals. The study carried out at 297, 273 and 253 K leads to a quantum yield φ{symbol}N O3 = 0.18 ± 0.03, and φ{symbol}N O2 + φ{symbol}N O3 = 1.01 ± 0.09. To minimize the errors in both the determination of quantum yields and the analysis of atmospheric photochemical lifetimes, the study of the absorption cross-sections dependence with temperature between 297 and 245 K was undertaken. There is a clear increase of the cross-sections with temperature. The atmospheric photochemical lifetime of CF3OC(O)OONO2 and its comparison with thermal decomposition are presented. © 2009 Elsevier B.V. All rights reserved.Fil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Manetti, Martin Diego. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Chiappero, Malisa Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Gallay, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Argüello, Gustavo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentin